全文获取类型
收费全文 | 313篇 |
免费 | 18篇 |
专业分类
化学 | 247篇 |
晶体学 | 5篇 |
力学 | 2篇 |
数学 | 6篇 |
物理学 | 71篇 |
出版年
2024年 | 2篇 |
2023年 | 4篇 |
2022年 | 2篇 |
2021年 | 5篇 |
2020年 | 2篇 |
2019年 | 6篇 |
2018年 | 4篇 |
2017年 | 2篇 |
2016年 | 7篇 |
2015年 | 7篇 |
2014年 | 13篇 |
2013年 | 16篇 |
2012年 | 26篇 |
2011年 | 15篇 |
2010年 | 7篇 |
2009年 | 11篇 |
2008年 | 17篇 |
2007年 | 20篇 |
2006年 | 17篇 |
2005年 | 14篇 |
2004年 | 7篇 |
2003年 | 14篇 |
2002年 | 8篇 |
2001年 | 8篇 |
2000年 | 6篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 8篇 |
1992年 | 5篇 |
1991年 | 2篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1978年 | 9篇 |
1977年 | 3篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1970年 | 2篇 |
1968年 | 1篇 |
1967年 | 3篇 |
1964年 | 1篇 |
排序方式: 共有331条查询结果,搜索用时 15 毫秒
1.
High-resolution vibrational electron energy loss spectroscopy, low-energy electron diffraction and Auger electron spectroscopy have been used to study the interactions of nitrogen with the Pd(110) surface. At 120 K, N2 is chemisorbed molecularly on the Pd(110) surface, and the (2 × 1)-N2 structure is formed. Most probably, the N2 molecules are chemisorbed in the on-top sites of the bulk-like Pd(110) surface in the upright-linear structure. The Pd---N2 bond energy is estimated to be ˜ 6 kcal/mol. The Pd---N2 and N---N stretching vibrations of N2 admolecules on Pd(110) are observed at 30 and 278 meV, respectively. The primary-energy dependence and angle dependence of their excitation cross sections agree reasonably well with the prediction of the dipole theory. The electron beam-induced effects are briefly discussed. 相似文献
2.
Masaaki Kubota Raul A. Reimer Kuniko Terajima Yuji Yoshimura Akio Nishijima 《Analytica chimica acta》1987
Inductively-coupled plasma/atomic emission spectrometry with a high-resolution vacuum scanning monochromator is described for the determination of sulfur at 180.734 nm. The behavior of the signal-to-background ratio is investigated as functions of RF power, argon gas flow rate and observation height above the load coil. Under the operating conditions selected, the detection limit is 3 μg l?1. The Se I 196.090-nm line is chosen as internal standard, because the S/Se line pair exhibited the least change with carrier gas flow rate and acid concentration of solution. Sulfur in NiMo and CoMo/ Al2O3 catalysts used for coal liquefaction is determined as S(II) and S(VI) species. The total amount of the species agreed well with the sulfur value obtained by the conventinal combustion method. 相似文献
3.
Toru Egawa Yukari Kachi Tsuguhide Takeshima Hiroshi Takeuchi Shigehiro Konaka 《Journal of Molecular Structure》2003,658(3):241-251
The molecular structure and conformation of carvone, a compound with a minty odor, were investigated by means of gas electron diffraction supported by theoretical calculations. Electron diffraction patterns were recorded by heating the nozzle up to 128 °C to obtain enough scattering intensity. The infrared spectrum was also measured by using an absorption cell with a path length of 10 m. The obtained molecular scattering intensities were analyzed with the aid of theoretical calculations and infrared spectroscopy. It was revealed that the experimental data are well reproduced by assuming that carvone consists of a mixture of three conformers that have the isopropenyl group in the equatorial position and mutually differ in the torsional angle around the single bond connecting the ring and the isopropenyl group. It was also found that the puckering amplitude of the ring of carvone is close to those of menthol and isomenthol, a minty compound and its nonminty isomer. The determined structural parameters (rg and ∠α) of the most abundant conformer of carvone are as follows: 〈r(C-C)〉=1.520(3) Å; 〈r(CC)〉=1.360(5) Å; r(CO)=1.225(5) Å; 〈r(C-H)〉=1.104(4)Å; 〈∠CC-C〉=121.1(5)°; 〈∠C-C-C〉=110.4(5)°; ∠C-CO-C=117.1(14)°; 〈∠C-C-H〉=111.1(13)°. Angle brackets denote average values and parenthesized values are the estimated limits of error (3σ) referring to the last significant digit. 相似文献
4.
Shin-ichiro Shoda Yoshinori Misawa Yousuke Nishijima Yukiko Tawata Tomohiko Kotake Masato Noguchi Atsushi Kobayashi Takeshi Watanabe 《Cellulose (London, England)》2006,13(4):477-484
Chitinase-catalyzed hydrolytic and transglycosylating behavior of 1,2-oxazoline derivative of N-acetyllactosamine (LacNAc-oxa) 1 has been investigated. An extremely rapid hydrolysis (ring-opening of the oxazoline moiety) could be observed, suggesting that 1 behaves as a transition state analogue substrate for chitinase A1 (Bacillus circulans WL-12). This disaccharide monomer 1 was found to polymerize under basic conditions, giving rise to novel oligosaccharides having a β(1-4)–β(1-6) repeating unit in the main chain. The degree of polymerization of the resulting oligosaccharides was up to 5. This is the first example of enzymatic glycosylation reaction forming a β(1-6) bond catalyzed by chitinase. 相似文献
5.
Miyauchi M Hoshino T Yamaguchi H Kamitori S Harada A 《Journal of the American Chemical Society》2005,127(7):2034-2035
A [2]rotaxane capped by a beta-cyclodextrin and a 2,4,6-trinitrophenyl group has been prepared by dissolving 6-aminocinnamoyl beta-cyclodextrin in water with 1-adamantane carboxylic acid and complexation with alpha-cyclodextrin followed by the reaction with 2,4,6-trinitrobenzene sulfonic acid sodium salt. The [2]rotaxane has been found to form supramolecular polymers by host-guest interactions. 相似文献
6.
During the search for polyketide synthase (PKS) in the genome of Streptomyces halstedii HC34, we found clustered new genes which appeared to encode typical Type 1 PKSs beyond the cluster harboring the genes for the biosynthesis of antitumor antibiotic vicenistatin. The deduced domain configuration of these putative PKS genes allowed to predict a corresponding partial structure of polyketide, which was in turn materialized by isolation of new polyketide macrolactone halstoctacosanolides A and B from the fermentation broth of S. halstedii HC34. The structures of these metabolites were determined by spectroscopic means to have a novel 28-membered macrolactone structure. The partial structure deduced from the genetic data was completely compatible to the structures of halstoctacosanolides A and B. This success clearly demonstrates the present new approach of genome-inspired search for new antibiotics promising. Halstoctacosanolides A and B showed moderate antimicrobial activity against several microorganisms. 相似文献
7.
Chitosan was partially N‐acylated by treatment with n‐fatty acid anhydrides in a homogeneous solution in 2 vol.‐% aqueous acetic acid‐methanol (1:2 v/v). The degree of substitution (d.s.) for N‐acyl groups in the water‐soluble N‐acylchitosan derivatives was in the range of 0.42–0.82 for N‐acetyl, 0.37–0.76 for N‐propionyl, 0.52–0.71 for N‐butyryl and 0.54–0.64 for N‐pentanoyl and ca. 0.58 for N‐hexanoyl, respectively.
8.
Nabeshima T Tsukada N Nishijima K Ohshiro H Yano Y 《The Journal of organic chemistry》1996,61(13):4342-4350
Synthesis and metal binding properties of thiolariat ethers, where a sulfide side chain is introduced into a framework of a crown ether, have been performed. Remarkably high Ag(+) selectivity among heavy metal ions was observed in solvent extraction and transport across a liquid membrane using thiolariat ethers with a 15-crown-5 ring as carriers. Thiolariat ethers with a 12-crown-4 or a 18-crown-6 do not exhibit such a high Ag(+) selectivity. The former binds metal ions weakly, and the latter recognizes Pb(2+) as well as Ag(+). The corresponding oxygen analogs, i.e. lariat ethers, do not show Ag(+) selectivity. The Ag(+) binding strength of the sulfoxide and sulfone analogs is much lower than that of thiolariat ethers. Thiolariat ethers with a benzocrown framework containing a sulfide chain at the 4 position of the benzene nucleus showed very low affinity to Ag(+). Extractability and transport ability using various thiolariat ether derivatives strongly suggested that this high Ag(+) selectivity is a result of the synergistic coordination of the ring oxygen and the sulfur atom of the thiolariat ether. NMR chemical shifts of protons and carbons in the proximity of the sulfur atom of the thiolariat ether were changed significantly in accordance with the synergistic coordination described above. 1:1 Complexation between a thiolariat ether and Ag(+) were supported by a Job plot using the chemical shift of the methylene protons adjacent to the sulfur atom. 相似文献
9.
Neil C. Concibido Tetsuji Okuda Wataru Nishijima Mitsumasa Okada 《Reaction Kinetics and Catalysis Letters》2006,89(2):369-376
Summary The hydrodechlorination of tetrachloroethylene in methanol (MeOH) over palladium catalysts on activated carbon (Pd/C) at 20°C
and atmospheric pressure was rendered safer by using ethanol (EtOH), isopropanol (IPA) or water-alcohol mixtures as solvents.
Adding water to MeOH was better than using EtOH or IPA since it resulted in a faster reaction and better stability of Pd/C,
which could also be completely reactivated. 相似文献
10.
Hiroshi Takeuchi Makoto Nakagawa Takayuki Saito Toru Egawa Kiyoshi Tanaka Shigehiro Konaka Toshiyuki Mitsuhashi 《International journal of quantum chemistry》1994,52(6):1339-1348
The energy spectra of free water molecules were measured at scattering angles 2θ ranging from 10.5° to 75.7°, using an angle-dispersive-type diffractometer and synchrotron radiation as an X-ray source. A silicon (111) monochrometer was used to obtain incident X-rays with the wavelengths of (1.543/n) Å (n = 1,3,4,5). Observed inelastic scattering peaks are clearly separated from eleastic ones at s values [s = (4π/λ) sin Å] larger than 8 Å?1. The increase of the separation with an increasing s value was consistent with the classical theory of the Compton shift. The total (elastic plus inelastic) intensities were obtained over a range of s = 0.74–5.0 Å?1. Experimental difference intensities Δσee and Δσne were obtained separately by combining the X-ray and high-energy electron scattering data. The experimental results are in reasonable agreement with the theoretical intensities calculated from SCF and CI molecular wave functions with a basis set of double-zeta plus polarization functions. © 1994 John Wiley & Sons, Inc. 相似文献